Trisazo/azoxy dyestuff mixtures

ABSTRACT

Trisazo/azoxy dyestuff mixtures which in the form of free acid correspond to the formula ##STR1## in which R denotes H or optionally substituted alkyl, 
     X and Y denote H, alkyl, alkoxy, halogen, hydroxyl, alkylsulphonyl, optionally mono- or di-alkyl-substituted sulphamyl, carboxyl and carboxyalkoxy and 
     K denotes the radical of a coupling component, 
     are outstandingly suitable for dyeing fibre materials containing hydroxyl groups and fibre materials containing amide groups, such as cotton, natural and synthetic polyamide, paper and leather. They give dyeings having good build-up capacity and good combinability.

This is a continuation of application Ser. No. 267,812, filed 5/27/81(now abandoned).

The invention relates to trisazo/azoxy dyestuff mixtures which in theform of the free acid can be represented by the formula ##STR2## inwhich R denotes H or optionally substituted alkyl,

X and Y denote H, alkyl, alkoxy, halogen, hydroxyl, alkylsulphonyl,optionally mono- or di-alkylsubstituted sulphamyl, carboxyl andcarboxyalkoxy and

K denotes the radical of a coupling component.

K for example represents a coupling component from thehydroxybenzenesulphonic acid, hydroxybenzenecarboxylic acid, pyrazole orindole series, but especially the naphtholsulphonic acid series.

Trisazo/azoxy dyestuff mixtures which in the form of the free acidcorrespond to the formula ##STR3## in which R, X and Y have theabovementioned meaning and

R₁ represents hydrogen or optionally substituted alkyl,

are of particular importance.

Trisazo/azoxy dyestuff mixtures of the formulae (III), (IV) or (V)##STR4## in which R, R₁, X and Y have the meanings already mentioned

are also preferred.

Furthermore, trisazo/azoxy dyestuff mixtures which in the form of thefree acid correspond to the formula ##STR5## in which X and Y have theabovementioned meanings

are of particular importance.

R and R₁ preferably represent hydrogen or C₁ -C₄ -alkyl, which can forexample by substituted by --OH, --COOH or --SO₃ H. Examples which may bementioned are methyl, ethyl, carboxymethyl, 2-hydroxyethyl andsulphoethyl.

X and Y preferably represent hydrogen, C₁ -C₄ -alkyl, especially methyland ethyl, C₁ -C₄ -alkoxy, chlorine, bromine, hydroxyl, C₁ -C₄-alkylsulphonyl, especially methylsulphonyl, optionally mono- or di-C₁-C₄ -alkyl-substituted sulphamyl, COOH or --O--C₁ -C₄ -alkyl--COOH.

In the trisazo/azoxy dyestuff mixtures according to the invention, thedyestuffs can be in the form of the free acid or of its salts,especially the alkali metal salts and ammonium salts.

The preparation of the dyestuffs of the formulae (I) to (VI) is carriedout by reducing monoazo compounds containing nitro groups, or mixturesof monoazo compounds containing nitro groups, of the formula (VII) or ofthe formula (VIII), or mixtures of the monoazo compounds of the formulae(VII) and (VIII), or (VII) and (IX) or (VIII) and (IX) ##STR6## whereinR, R₁, X and Y, as well as K, have the meaning already given,

in an aqueous alkaline medium at temperatures of between 30° and 90° C.,by means of a reducing agent, such as, for example, glucose,hydrazine/catalyst, hydrazine/active charcoal, sodium sulphite solution,sodium sulphide and the like and at the same time effecting condensationto the trisazo and azoxy compounds (see Houben-Weyl, Volume 10/3, pages346-354).

In a preferred embodiment, after the reduction has been carried out,possible secondary components are additionally oxidised to thetrisazo/azoxy dyestuffs of of the formula (I) by means of one of thecustomary oxidising agents, for example chlorite bleach or hydrogenperoxide, if appropriate in the presence of metals. This subsequentoxidation as a rule leads to a relatively pure dyestuff.

The choice of optimum oxidation conditions and the amount of oxidisingagent is in accordance with the nature and quality of the crude dyestuffformed, and must be established by simple preliminary experiments(compare also Example 1).

Suitable oxidising agents are all the reagents mentioned in Houben-Weyl,Volume 10/3, page 371 et seq., but preferably halogen-containing andoxygen-containing oxidising agents, such as, for example, halogens,hypochlorites, persulphates, perborates, permanganates, chromic acid,hydrogen peroxide, glacial acetic acid/hydrogen peroxide and glacialacetic acid/hydrogen peroxide/boric acid.

The use of chlorine, chlorite bleach or hydrogen peroxide under alkalineaqueous conditions, preferably at pH values of about 9 to about 12,proves particularly suitable.

Preferably, the oxidation is carried out at temperatures of about 30° C.to about 80° C.

The nitroazo compounds of the formula (VII), (VIII) or (IX) are preparedby coupling diazotised 3- or 4-nitroaminobenzenes of the formula (X)with optionally N-substituted amino-naphtholsulphonic acids of theformula (XI), under acid conditions, in the ortho-position to the aminogroup, or with a coupling component KH. ##STR7## X, Y, R, R₁ and K havethe meanings already mentioned.

Examples of suitable compounds of the formula (X) are 3-nitroaniline,4-nitroaniline, 2-methyl-5-nitroaniline, 2-methyl-4-nitroaniline,2-methoxy-5-nitroaniline, 2-methoxy-4-nitroaniline,2-ethoxy-5-nitroaniline, 2-ethoxy-4-nitroaniline,2-chloro-5-nitroaniline, 2-chloro-4-nitroaniline,2-bromo-4-nitroaniline, 2-hydroxy-4-nitroaniline,2-methanesulphonyl-5-nitroaniline, 2-methanesulphonyl-4-nitroaniline,2-(N-ethyl-N-phenyl)-sulphonamido-5-nitroaniline,2-(N-ethyl-N-phenyl)-sulphonamido-4-nitroaniline,2-amino-4-nitrobenzenesulphonic acid, 2-amino-4-nitro-benzoic acid,2-amino-5-nitrobenzoic acid, (2'-amino-5'-nitrophenyl)-acetic acid and(2'-amino-5'-nitro)-phenoxy acetic acid.

Examples of suitable compounds of the formula (XI) are7-amino-1-hydroxy-naphthalene-3-sulphonic acid,7-amino-1-hydroxy-naphthalene-4-sulphonic acid,7-N-methylamino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-ethylamino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-propylamino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-butylamino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-(2'-hydroxyethyl)-amino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-(2'-sulphoethyl)-amino-1-hydroxy-naphthalene-3-sulphonic acid,7-N-(carboxymethyl)-amino-1-hydroxy-naphthalene-3-sulphonic acid and7-N-(2'-carboxyethyl)-amino-1-hydroxy-naphthalene-3-sulphonic acid.

Selected examples of coupling components K-H are5-amino-1-hydroxy-naphthalene-2-sulphonic acid,6-amino-1-hydroxy-naphthalene-2-sulphonic acid,5-amino-1-hydroxy-naphthalene-3-sulphonic acid,6-amino-1-hydroxy-naphthalene-3-sulphonic acid,4-hydroxy-7-(methylamino)-naphthalene-2-sulphonic acid,7-(diethylamino)-4-hydroxy-naphthalene-2-sulphonic acid,4-hydroxy-7-(phenylamino)-naphthalene-2-sulphonic acid,7-(acetylamino)-4-hydroxy-naphthalene-2-sulphonic acid,8-amino-1-hydroxy-naphthalene-3-sulphonic acid,4-amino-5-hydroxy-naphthalene-1-sulphonic acid,4-amino-5-hydroxy-naphthalene-1,6-disulphonic acid,2-amino-5-hydroxy-naphthalene-1,7-sulphonic acid,4-amino-5-hydroxy-naphthalene-1,7-sulphonic acid,4-amino-5-hydroxy-naphthalene-2,7-disulphonic acid,4-(ethylamino)-5-hydroxy-naphthalene-2,7-disulphonic acid,7-amino-3-hydroxy-naphthalene-1-sulphonic acid,4-amino-6-hydroxy-naphthalene-2-sulphonic acid,6-amino-7-hydroxy-naphthalene-2-sulphonic acid,5-amino-7-hydroxy-naphthalene-2-sulphonic acid,4-amino-7-hydroxy-naphthalene-2-sulphonic acid,6-amino-2-hydroxy-naphthalene-1,4-disulphonic acid,8-amino-3-hydroxy-naphthalene-1,6-disulphonic acid,8-amino-3-hydroxy-naphthalene-1,5-disulphonic acid,7-amino-6-hydroxy-naphthalene-1,3-disulphonic acid,1-hydroxy-naphthalene-2-disulphonic acid,4-hydroxy-naphthalene-2-sulphonic acid,4-hydroxy-naphthalene-1-sulphonic acid, 5hydroxy-naphthalene-1-sulphonicacid, 4-hydroxy-naphthalene-2,7-disulphonic acid,4-hydroxy-naphthalene-2,6-disulphonic acid,8-hydroxy-naphthalene-1,6-disulphonic acid,3-hydroxy-naphthalene-1-sulphonic acid,6-hydroxy-naphthalene-2-sulphonic acid,7-hydroxy-naphthalene-2-sulphonic acid,3-hydroxy-naphthalene-2,7-disulphonic acid,3-hydroxy-naphthalene-2,6-disulphonic acid,7-hydroxy-naphthalene-1,3-disulphonic acid,4,5-dihydroxy-napthalene-2,7-disulphonic acid, 2-hydroxybenzoic acid,3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 5-chloro-2-hydroxybenzoicacid, 2-hydroxy-4-methylbenzoic acid, 2,4-dihydroxybenzoic acid,4-hydroxy-1,3-benzenedicarboxylic acid, 2-hydroxy-benzenesulphonic acid,3-hydroxy-benzenesulfonic acid, 4-hydroxy-benzenesulphonic acid and thelike.

The dyestuffs of the formulae (I) to (VI) are used for dyeing fibrematerials containing hydroxyl groups and fibre matrials containing amidegroups, such as cotton, silk, natural and synthetic polyamide, paper andleather.

Thus, for example, dyestuffs according to formula (III), (V) and (VI)dye polyamide materials or cotton in violet, navy blue, greenish-tingedblue and black shades having good to very good fastness properties.(Details are to be found in the tables and examples).

Predominantly red and brown dyeings on textile materials are obtained onusing dyestuffs of the formula (IV).

The dyestuffs furthermore have good build-up capacity and goodcombinability. They can be employed in mixtures with other dyestuffs,for example for black mixtures.

EXAMPLE 1 ##STR8##

336 g of p-nitroaniline are diazotised with 780 ml of hydrochloric acidand 160 g of sodium nitrite at 8°-14° C., in aqueous solution (volumeabout 10 l). The excess nitrite is destroyed with amidosulphonic acidand the mixture is clarified. A solution of 552 g of7-amino-1-hydroxy-naphthalene-3-sulphonic acid in 750 ml of water and1.5 l of 20 percent strength sodium carbonate solution is added dropwisein the course of 1 hour at 10° C. The coupling mixture is stirred for 2hours and neutralised with 900 ml of sodium carbonate solution. Thereaction mixture is heated to 65° C. and brought to pH 12.5 with 900 mlof concentrated sodium hydroxide solution, and 300 g of glucose areadded. The reduction takes place slightly exothermically, as shown bythe temperature rising to 68° C. The reaction mixture is kept at 65°-70°C. for a further 30 minutes (pH: about 11.5). The product is salted outwith 540 g of sodium chloride. To oxidise the red by-product, 1.3 l ofchlorite bleach (about 13% of active chlorine) are added rapidly, at 65°C., and stirring is continued for 30 minutes. The mixture is renderedneutral by adding 450 ml of hydrochloric acid and, after addition ofabout 360 g of sodium chloride is stirred for a further hour, and theproduct is filtered off at 60° C. After isolation and drying, about 850g of a dyestuff which dyes synthetic polyamide (polyamide 6) in a navyblue shade having very good general fastness properties (λ_(mmax) =573nm) are obtained. (All λ_(max) values relate to water as the solvent).

The dyestuffs characterised in the tables which follow are also preparedanalogously to the procedure described in Example 1. (PA=syntheticpolyamide, CO=cotton). ##STR9##

                                      TABLE 1                                     __________________________________________________________________________                                           Shade (dyed                            No.                                                                              R       R.sub.1 X         Y         material)                                                                              λ .sub.max.sup.[nm]    __________________________________________________________________________    2  H       H       CH.sub.3  CH.sub.3  navy blue (PA)                                                                         573                           3  H       H       Cl        Cl        navy blue (PA)                                                                         595                           4  H       H       Br        Br        navy blue (PA)                                                                         598                           5  H       H       OCH.sub.3 OCH.sub.3 greenish-tinged                                                                        617                                                                  blue (PA)                              6  H       H       SO.sub.2 CH.sub.3                                                                       SO.sub.2 CH.sub.3                                                                       blue (PA)                                                                              608                           7  H       H                                                                                                ##STR10##                                                                              greenish-  tinged blue                                                                 623)                          8  CH.sub.3                                                                              CH.sub.3                                                                              H         H         blue (PA)                                                                              588                           9  CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                                  H         H         blue (PA)                                                                              591                           10 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CO.sub.2 H                                                                   H         H         blue (PA) (Co)                         11 CH.sub.2 CH.sub.2 SO.sub.3 H                                                          CH.sub.2 CH.sub.2 SO.sub.3 H                                                          H         H         blue (Co)                                                                              591                           12 CH.sub.3                                                                              CH.sub.3                                                                              Cl        Cl        navy blue (PA)                         13 H       H       CO.sub.2 H                                                                              CO.sub.2 H                                                                              blue (Co)                              14 H       H       OCH.sub.2CO.sub.2 H                                                                     OCH.sub.2CO.sub.2 H                                                                     greenish-                                                                     tinged blue (Co)                       15 CH.sub.3                                                                              CH.sub.3                                                                              SO.sub.3 H                                                                              SO.sub.3 H                                                                              blue (Co)                              16 CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                                  SO.sub.3 H                                                                              SO.sub.3 H                                                                              blue (Co)                                                                     (paper)                                17 CH.sub.2 CH.sub.2 SO.sub.3 H                                                          CH.sub.2 CH.sub.2 SO.sub.3 H                                                          OCH.sub.3 OCH.sub.3 greenish-                                                                     tinged blue (Co)                                                              (paper)                                18 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CO.sub.2 H                                                                   OCH.sub.3 OCH.sub.3 greenish-                                                                     tinged blue (CO)                       19 CH.sub.3                                                                              H       H         H         navy blue (PA)                         20 CH.sub.3                                                                              H       CH.sub.3  H         navy blue (PA)                         21 CH.sub.3                                                                              CH.sub.3                                                                              OCH.sub.3 OCH.sub.3 blue (PA)                              22 CH.sub.3                                                                              CH.sub.3                                                                              SO.sub.2 N(C.sub.2 H.sub.5)(C.sub.6 H.sub.5)                                            SO.sub.2 N(C.sub. 2 H.sub.5)(C.sub.6                                          H.sub.5)  greenish-                                                                     tinged blue (PA)                       23 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       H         H         navy blue (PA)                         24 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       Cl        Cl        navy blue (PA)                         25 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       CO.sub.2 H                                                                              CO.sub.2 H                                                                              blue (CO) (PA)                         __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR11##                                 (IV)                               No.                                                                              R       R.sub.1 X  Y  Shade (dyed material)                                                                        [nm]                                                                             λ.sub.max                   __________________________________________________________________________    26 H       H       H  H  red      (PA)  500                                   27 H       H       CH.sub.3                                                                         CH.sub.3                                                                         bluish-tinged red                                                                      (PA)  504                                   28 CH.sub.3                                                                              CH.sub.3                                                                              H  H  red      (PA)                                        29 CH.sub.3                                                                              CH.sub.3                                                                              CH.sub.3                                                                         CH.sub.3                                                                         bluish-tinged red                                                                      (PA)                                        30 CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                                  H  H  bluish-tinged red                                                                      (PA)                                        31 CH.sub.2 CH.sub.2 OH                                                                  CH.sub.2 CH.sub.2 OH                                                                  CH.sub.3                                                                         CH.sub.3                                                                         bluish-tinged red                                                                      (PA)                                        32 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CO.sub.2 H                                                                   H  H  bluish-tinged red                                                                      (PA) (CO)                                   33 CH.sub.2 CO.sub.2 H                                                                   CH.sub.2 CO.sub.2 H                                                                   CH.sub.3                                                                         CH.sub.3                                                                         bluish-tinged red                                                                      (PA) (CO)                                   34 CH.sub.2 CH.sub.2 SO.sub.3 H                                                          CH.sub.2 CH.sub.2 SO.sub.3 H                                                          H  H  bluish-tinged red                                                                      (CO)                                        35 CH.sub.2 CH.sub.2 SO.sub.3 H                                                          CH.sub.2 CH.sub.2 SO.sub.3 H                                                          CH.sub.3                                                                         CH.sub.3                                                                         bluish-tinged red                                                                      (CO)                                        __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR12##                                                                    No.                                                                              R X   Y   K             Shade/λ.sub.max [nm]                        __________________________________________________________________________    36 H H   H                                                                                  ##STR13##    blue (PA/CO)/582                                   37 H H   H                                                                                  ##STR14##    navy blue (PA/CO)/587                              38 H H   H                                                                                  ##STR15##    violet (PA)/560                                    39 H H   H                                                                                  ##STR16##    greenish-tinged blue (PA) blue (CO) 588            40 H H   H                                                                                  ##STR17##    greyish blue (PA)/572                              41 H H   H                                                                                  ##STR18##    blue-black (PA) violet (CO)/578                    42 H H   H                                                                                  ##STR19##    blue (PA) reddish-tinged blue (CO)/578             43 H H   H                                                                                  ##STR20##    violet (CO/PA)/561                                 44 H H   H                                                                                  ##STR21##    blue (PA/CO)/575                                   45 H H   H                                                                                  ##STR22##    blue (PA) violet (CO)/580                          46 H OCH.sub.3                                                                         OCH.sub.3                                                                          ##STR23##    strongly greenish-tinged blue (PA)/605             47 H OCH.sub.3                                                                         OCH.sub.3                                                                          ##STR24##    blue (PA) reddish-tinged blue (CO)/ 585            48 H OCH.sub.3                                                                         OCH.sub.3                                                                          ##STR25##    greenish-tinged blue (PA) blue                     __________________________________________________________________________                               (CO)/622                                       

                  TABLE 4                                                         ______________________________________                                         ##STR26##                                                                                                         Shade/λ.sub.max                   No.  R     X     Y   K               [nm]                                     ______________________________________                                        49   H     H     H                                                                                  ##STR27##      reddish-tinged violet (PA) claret                                             (CO)/527                                 50   H     H     H                                                                                  ##STR28##      red-brown (PA)/502                       51   H     H     H                                                                                  ##STR29##      violet (PA/CO)/525                       52   H     H     H                                                                                  ##STR30##      red-brown (PA)/502                       53   H     H     H                                                                                  ##STR31##      bluish-tinged red (PA) red (CO)/515      54   H     H     H                                                                                  ##STR32##      red-brown (PA)/504                       ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR33##                                                                                                            Shade/                                No.  R     X       Y     K              λ.sub.max                      ______________________________________                                                                                [nm]                                  55   H     H       H                                                                                    ##STR34##     reddish- tinged violet (PA)/531       56   H     H       H                                                                                    ##STR35##     navy blue (PA)/543                    57   H     OCH.sub.3                                                                             OCH.sub.3                                                                            ##STR36##     navy  blue (PA)/539                   58   H     OCH.sub.3                                                                             OCH.sub.3                                                                            ##STR37##     blue (PA)/540                         ______________________________________                                    

We claim:
 1. A trisazo/azoxy dyestuff mixture which in the form of thefree acid correspond to the formula ##STR38## and X and Y denote H, C₁-C₄ -alkoxy, chlorine, bromine, C₁ -C₄ -alkylsulphony, sulphamyl,mono-C₁ -C₄ -alkyl sulphamyl, di-C₁ -C₄ -alkyl sulphamyl, carboxyl orcarboxy C₁ -C₄ -alkoxy.